Uretidinedione fungicides



United States Patent 3,223,584 URETIDINEDIONE FUNGHJIDES Raymond W. Luclrenbaugh and Kenneth C. Smeltz, Wilmington, Del., assignors to E. I. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware No Drawing. Filed Mar. 18, 1964, Ser. No. 352,997 9 Claims. (Cl. 16733) This invention relates to the use of 1,3-diphenyl or di (substituted phenyl -2,4-uretidinediones.

More specifically, this invention refers to a method for the control of foliar fungi by applying to foliar surfaces or fungi attacking foliage a fungicidal amount of a 1,3-diphenyl or di(substituted phenyl)-2,4-uretidinedione.

Scientific endeavor continues to assault the enemies of mankind. Only through the development of new fungicides having a particularly toxic effect on fungi and low human toxicity can man expect to rid himself of fungicidal pests. The Erysiphaceae or powdery mildew fungi are a serious problem to man. They are hard-to-kill, obligate parasites of higher plants. Frequently these same higher plants are important human foods. Such crops as grapes, hops, gooseberries, roses and other ornamentals, clovers, apples, cucumbers, cantaloupe, watermelon and cereal plants are affected. Altogether the total number of plants infected by these fungi number more than 150 species.

We have found that the compounds or mixtures of the compounds set forth below are effective in controlling powdery mildew fungi and Venturia inaequalis the apple scab fungus as well as other fungi affecting the foliage of plants. Some of these compounds control the Pythium species which cause damping off of plant seedlings. These compounds are described in the following structure:

wherein X and Y are the same or different and can be hydrogen, chlorine, fluorine, and methyl.

Preferred compounds include the following:

1,3 -di (4-chloro'phenyl -2,4-uretidinedione 1,3-di (4-tolyl)-2,4-uretidinedione l-phenyl-3-(4-chlorophenyl)-2,4-uretidinedione 1- 4-tolyl -3 -phenyl-2,4-uretidinedione 1,3-diphenyl-2,4-uretidinedione figuration, that is, 4-imino-1,3-oxazetidine-2-one.

The foliar fungicidal compounds of this invention are well known in the literature as intermediates in the preparation of adhesives and other materials widely used in the textile, paper, leather, rubber and related trades.

One method of preparation is described in Stallmann US. Patent No. 2,671,082.

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COMPOSITIONS Compounds used in this invention can be formulated into compositions which can include surface-active agents,

pulverulent diluents and solvents.

A surface-active agent or surfactant can include any of the anionic, cationic and non-ionic surface-active agents. Suitable surface-active agents are set out, for example in Searle US. Patent 2,426,417; Todd US. Patent 2,655,447; Jones US. Patent 2,412,510; or Lenher US. Patent 2,139,276. A detailed list of such agents is set forth in Detergents and Emulsifiers Annual, 1963, by John W. McCutcheon, Inc., and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the US. Department of Agriculture.

Anionic and non-ionic surfactants are preferred. Among the anionic surfactants, preferred ones include alkali and alkaline earth salts of alkylaryl sulfonic acids, e.g. dodecylbenzenesulfonates and alkyl naphthalene sulfonates, dialkyl sodium succinate esters, sodium lauryl sulfate, sodium N-methyl-N-oleoyl taurate, sodium dodecyldiphenyl ether disulfonate and the oleic ester of sodium isethionate.

The preferred non-ionic surfactants include ethylene oxide adducts with octylphenol, nonylphenol, dodecyl phenol, sorbitan fatty acid esters and long chain alcohols and mercaptans as well as poly(ethyleneoxy)esters of fatty acids.

Preferred dispersants for wettable powders and aqueous suspensions are alkali and alkaline earth lignin sulfonates and the salts of polymerized alkylaryl sulfonic acids which are sold under the Darvan and Daxad trademarks, as well as methyl cellulose, polyvinyl alcohols and the like.

Surfactants are present in compositions of this invention in the range of 0.1 to 20% by weight.

The compositions can also contain, with or without surfactant, a finely divided solid diluent such as talc, clays, including kaolinite and attapulgite, pyrophyllite, diatomaceous earth, synthetic silicas, calcium silicate, calcium sulfate and flours derived from natural sources such as walnut shell, redwood, cotton seed and the like.

Particle size of the inert extender can vary considerably but will ordinarily be somewhat under 50 microns in the finished formulation.

Dust compositions contain 1 to 30% by weight of the active ingredient. However, 3 to 15% by weight is preferred.

In wettable powder compositions containing the active ingredient, one or more surfactants and a finely divided inert diluent as described above, the active compound ordinarily is present in a concentration range of 25 to by weight. Surfactants are present in the range of 0.1 to 10% by weight to obtain adequate wetting and dispersion in water with the remainder being largely one or more of the-finely divided diluents shown above.

Wettable powders are prepared by mixing the ingredients in a blender and grinding the mixture in a hammer mill, air-impact mill or the like until the particle size has been reduced to make spray application practical and easy.

Wettable powders and liquid compositions are frequently used by dilution and extension with ,water to form spray slurry compositions containing from 0.05 to 3% of the active ingredient.

Suspension compositions can be prepared by combining one or more of the active ingredients used in this invention together with paraffinic hydrocarbons, aromatic hydrocarbons or mixtures thereof or halogenated hydrocarbons. In liquid compositions there is present 1 to 50% by weight of active ingredient used in this invention.

Compositions of this invention can additionally con- Metal salts of ethylene bisdithiocarbamic acid, e.g. Manganese, zinc, iron and sodium salts; 5 Ethylene thiuram monosulfide;

Dodecylguanidine acetate; N-trichloromethylthiotetrahydrophthalimide (Captan); Phenylmercury acetate;

2,4-dichloro-6- o-chloroanilino) -s-triazine; N-methyhnercury p-toluenesulfonanilide; Methylmercury acetate;

Methylmercury 2,3-dihydroxypropyl mercaptide; 3,3-ethylenebis(tetrahydro-4,6-dimethyl-2H-1,3,5-

thiadiazine-Z-thione) Methylmercury dicyandiamide; N-ethylmercury-p-toluenesulfonanilide;

Metal (e.g., iron, sodium and zinc), .ammonium and amine salts of dialkyldithiocarbamic acids,

for instance ziram and ferbam; Copper-S-quinolate;

Copper dihydrazinium sulfate;

2-heptadecylglyoxalidine acetate;

Tetra copper calcium oxychloride;

Methylmercury nitriles; 2,3-dichloro-1,4-naphthoquinone;

Tetrachloroquinone; and

N-trichloromethylthiophthalimide (Phaltan).

Fungicides such as the above are added to compositions containing the active ingredient used in this invention at the rate of 1 to 400 pounds to each 20 pounds of a compound used in this invention. Fungicides used at loW rates with the active ingredients of this case are, for example, manganese or Zinc ethylenebis(dithiocarbamate). Illustrative of a fungicide used at high rates with the active ingredients of this case is captan. Of course, more or less of the above-listed fungicides can be added to a composition of this invention depending on the fungi present in the area to be protected.

Compositions of this invention can additionally contain insecticides such as:

Guthion, 0,0-dimethyl-S-4-oxo-1,2,3-benzotriazin-3- (4H) -ylmethyl phosphorodithioate Rotenone S-[ 1,2-bis (ethoxycarbonyl) ethyl] -0,0-dimethylphosphorodithioate (malathion) Sevin, 1-naphthyl-N-methylcarbamate 0,0-diethyl-O-p-nitrophenyl phosphorothioate (parathion) Lindane Diazinon, 0,0-diethyl-O-(2-isopropyl-4Inethyl-6- pyrimidyl phosphorothioate Kelthane, 4,4'-dichloro-u-trichloromethylbenzhydrol Nicotine .Lead arsenate DDT Methoxychlor and others for simultaneous control of insects and fungi on plants. 7

From 0.1 to 10 parts by weight of the insecticide is used for each one part by weight of the disulfides used in this invention.

In addition compositions can contain special additives such as corrosion inhibitors, pigments, antifoam agents and the like.

APPLICATION The active compound used in this invention is sprayed or dusted to give complete coverage of the plant tissue Which is to be protected. By applying the active ingreclient before the infection is noted or anytime up to three days after infection is begun, adequate control of the foliage fungi is obtained without any toxic effect on the plant itself. The active ingredient used in this invention is applied at the rate of 0.1 to 10 pounds per 100 gallons of spray mixture. In the case of dust compositions the active ingredient will ordinarily be applied at the rate of 0.1 to 20 pounds per acre.

Applications can be made with any conventional dust or spray equipment Well known in the art.

In addition to the examples set forth above the following examples are provided to more clearly describe this invention.

Example 1 Percent 1,3-diphenyl-2,4-uretidinedione Calcined montmorillonite 20 The ingredients are blended in a ribbon blender and then passed through a micropulverizer to reduce the particle size substantially all below 50 microns Generally this dust concentrate is intimately mixed further with talc or other such available inert powders at the rate of 10% by Weight ofthe concentrate described above and by Weight of the talc. This diluted mix is passed through a micropulverizer.

Employing a commercial duster the diluted dust is applied to a field of cantaloupes at 40 to 80 pounds per acre as soon as powdery mildew is first reported in the area. The application is repeated at 4 to 6 day intervals throughout the growing period. Outstanding control of powdery mildew, Erysiphe eichoracearum D.C., is obtained with a corresponding increased yield of high quality cantaloupes.

Examples 25 A like amount by weight of the following compounds are substituted one at a time for the 1,3-diphenyl-2,4- uretidinedione of Example 1. They are each formulated and applied in like manner to give like results.

(2) 1,3-di (m-chlorophenyl -2,4-uretidinedione (3) 1- o-fluorophenyl -3-phenyl-2,4-uretidinedione (4) 1- (m-tolyl -3- (p-tolyl -2,4-uretidinedione (5) 1,3 -di (m-fluorophenyl -2,4-uretidinedione Example 6 Percent 1,3-di(m-tolyl)-2,4-uretidinedione 3.0 Sodium dioctylsulfosuccinate 0.5 Polymerized alkylarylsulfonates 1.0

Pyrophyllite 95.5

The ingredients are blended in an eflicient mechanical mixer and micropulverized to produce particles substantially all below 40 microns.

Generally 80 to pounds per acre of the above formulation is applied to a field of cantaloupes as described in Example 1. Like results are obtained.

Example 7 Percent 1,3-di(p-tolyl)-2,4-uretidinedione 10 Micaceous talc 90 The active ingredient is pre-ground until all particles are substantially below 40 microns. It is then blended with the diluent.

The above formulation is applied with a hand duster at a rate of 40 to 80 pounds per acre to give complete coverage of the foliage of a commercial planting of grapes. Treatments are repeated at 4 to 7 day intervals throughout the crop period. Control is achieved over powdery mildew resulting in an increased yield of high grade fruit.

Example 8 Percent Dust concentrate (75%) of 1-(p-ch1orophenyl)-3- phenyl-2,4-uretidinedione 20 Powdered pyrophyllite 80 Before packaging, the material is intimately mixed by passage throughout a micropulverizer.

This dust formulation is applied to a field of barley at rates of 40 to 80 pounds per acre. Applications are initiated as soon as either rust or powdery mildew appear in the area. Applications are continued at weekly intervals as long as the crop is growing actively. Both powdery mildew and rust are controlled. High yields of good quality grain result.

Example 9 Percent 1,3-diphenyl-2,4-uretidinedione 20.0 Sodium dodecylbenzenesulfonate 0.5 Methylated cellulose 3.0

Kaolinite 81.5

The ingredients are thoroughly blended and passed through a micropulverizer to produce particles substantially all below 50 microns.

A Wettable powder of the above formulation is dispersed and diluted in water to give an active ingredient concentration of 1.5 to 3 pounds per 100 gallons of water and are sprayed on a commercial planting of apple trees. Applications are started early in the spring and continued on a standard local spray schedule in combination with required insecticides. Excellent control is obtained of apple scab, powdery mildew, cedar apple rust and insects, resulting in a high yield of top quality fruit.

Examples 10-15 A like amount by weight of the following compounds are substituted one at a time for the 1,3-diphenyl-2,4- uretidinedione in Example 9. They are each formulated and applied in like manner to give like results.

1,3-di p-fluorophenyl) -2,4-uretidinedione l-(p-chlorophenyl -3-phenyl-2,4-uretidinedione The dry ingredients are blended and passed once through a micropulverizer to produce particles substantially all below 100 microns. This powder is then fluid energy milled to produce particles substantially all below 7 microns.

A like amount by weight of this formulation based on active ingredient is substituted for the formulation of Example 9 and is applied in like manner. Like results are obtained.

Example 17 Percent 1,3-diphenyl-2,4-uretidinedione 73.8 NaH PO -I-I O 2.0 Sodium alkylnaphthalene sulfonate 3.0 Partially desultonated sodium lignin sulfonates 3.0 Kaolin clay 18.2

The ingredients are blended in an efiicient mechanical blender and then fluid energy milled until all particles are substantially below 5 microns.

A like amount of the above formulation based on active ingredient is substituted for the formulation of Example 9 and is applied in like manner. Similar results are obtained.

Example 18 Percent l-(p-chlorophenyl)-3-p-tolyl-2,4-uretidinedione 80 Ethylene oxide condensate with nonylphenol 3 Calcium lignin sulfonate 2 Montmorillonite 6 The ingredients are blended and micropulverized to yield a particle size substantially all below 40 microns.

A like amount by weight of this formulation is substituted for the formulation of Example 9 and is applied in like manner. Like results are obtained.

Example 19 Percent 3-(p-chlorophenyl) -l-phenyl-2,4-uretidinedione 15 .00 Sodium alkylnaphthalenesulfonate 1.00 Mixed sodium and calcium lignin sulfonate 6.00 Hydrated attapulgite 2.00 Monobasic potassium phosphate 1.00 Phenylmercury acetate u 0.25

Water 74.75

The slurry is sand ground in conventional equipment to produce particles substantially all below 5 microns in a stable suspension.

Sufficient of the above sand ground aqueous suspension is dispersed in water in a commercial sprayer tank to give an active ingredient concentration of 3 pounds per gallons. The foliage of hops in a commercial planting is sprayed with the resultant spray mixture. Applications are repeated as required in a standard spray schedule. Powdery mildew, Perolzoplasmorara humuli, is held in excellent check. Increased yields of high quality prodnet result. Similar untreated areas produce poor quality product.

Example 20 Percent 1,3-diphenyl-2,4-uretidinedione 35.5 Sodium lignin sulfonate 8.0 Hydrated attapulgite 1.5 Pentachlorophenol 0.5 Water 54.5

Example 21 Percent l-(p-fluorophenyl)-3-p-toly1-2,4-uretidinedione 50.0 Methylated cellulose 8.0 Pentachlorophenol 0.5 Water 42.5

The slurry is sand ground to produce a stable suspension of particles substantially all below 5 microns.

The above formulation is dispersed in water to give a concentration of 3 pounds of active ingredient per 100 gallons. This is sprayed on an oat field to give complete foliage coverage. Applications are started as soon as powdery mildew or rust becomes a threat in the area and are repeated at 7 to 14 day intervals for 2 to 4 applications. Excellent control of both rust and oat powdery mildew is obtained.

Example 22 Percent 1,3-diphenyl-2,4-uretidinedione 40 Polyoxyethylenesorbitol heptaoleate 8 Synthetic fine silica l Paraffinic hydrocarbon oil 51 The slurry is sand ground to produce a stable suspension of particles substantially all below 5 microns. The suspension is emulsifiable in water.

The formulation is then dispersed in water to provide 2.5 pounds per 100 gallons. It is then applied to a field 7 of watermelons. Sprays are started as soon as powdery mildew appears in the area and are repeated in combination with insecticides as required throughout the season. Powdery mildew is held in check. High yields result of The ingredients are thoroughly blended and micropulverized once to produce particles substantially all below 60 microns.

Employing a hand duster the formulation is applied to give thorough but light coverage of various flowers, fruit trees and shrubs in a home garden. Applications are repeated throughout the growing season at 4 to 7 day intervals. Excellent control is obtained of (l) powdery mildew on such plants as fire thorn, Zinnias and lilac; (2) rust on roses, dwarf apple trees, holly locks and the like; (3) scab on apples, fire thorn; black spot on roses and insects of various plants. Excellent development is obtained on foliage and flowers of treated plants.

Example 24 Percent Manganous ethylenebis(dithiocarbamate) 40 1,3-di-p-tolyl-2,4-uretidinedione 45 Sodium lignin sulfonate 1 Sodium alkylnaphthalene sulfonate 2 Kaolinite 12 The ingredients are blended and micropulverized to produce particles substantially all below 50 microns.

This formulation is dispersed in water to give 3 pounds of active ingredient per 100 gallons. The spray mixture is applied to a commercial planting of roses on a regular local spray schedule. Insecticides are added as required. Excellent control is maintained over powdery mildew, black spot and rust. A high yield of top quality flowers results.

Example 25 Percent 1,3-dipheny1-2,4-uretidinedione Methoxychlor, 90% commodity 12 Malathion, 25% wettable powder 34 Captan, 75% commodity Sodium lignin sulfonate 5 Dioctyl sodium sulfosuccinate 3 Calcined montmorillonite 16 The ingredients are blended and then micropulverized to produce particles substantially below 40 microns.

The above formulation is mixed in water to give 2 pounds of active ingredient per gallons. Sprays are applied in a standard spray schedule to a field of cucumbers. Insecticides are added as required. Commercial control of powdery mildew results. A high yield of cucumbers is obtained throughout the growing season.

The invention claimed is:

1. Method for the control of foliar fungi comprising applying to plant foliage a fungicidal amount of a compound of the formula wherein X and Y are separately selected from the group consisting of hydrogen, fluorine, chlorine and methyl.

2. Method for the control of foliar fungi comprising applying to said fungi a fungicidal amount of a compound of the formula wherein X and Y are separately selected from the group consisting of hydrogen, fluorine, chlorine and methyl.

3. Method according to claim 2 wherein the compound applied is 1,3-diphenyl-2,4-uretidinedione.

4. Method according to claim 2 wherein the compound applied is 1,3-di(4-chlorophenyl)-2,4-uretidinedione.

5. Method according to claim 2 wherein the compound applied is 1,3-di(4-tolyl)-2,4-uretidinedione.

6. Method according to claim 2 wherein the compound applied is 1-phenyl-3-(4-chloropheny1)-2,4-uretidinedione.

7. Method according to claim 2 wherein the compound applied is 1-(4-tolyl) -3-phenyl-2,4-uretidinedione.

8. Method according to claim 2 wherein said foliar fungi are of the taxonomic family Erysiphaceae.

9. Method according to claim 2 wherein said foliar fungi are of the genus Venturia.

No references cited.

JULIAN S. LEVITI, Primary Examiner. 

1. METHOD FOR CONTROL OF FOLIAR FUNGI COMPRISING APPLYING TO PLANT FOLIAGE A FUNGICIDAL AMOUNT OF A COMPOUND OF THE FORMULA 